Patent GB-777600-A (GB)
Title: Fungicidal and insecticidal compounds and compositions
Filed: 1954-10-25
Abstract: Complex double salts of rosin amines, as hereinafter defined, are prepared by reacting a rosin amine complex and a water-insoluble metal soap, in the presence or absence of a solvent, at a temperature at least sufficient to render the mixture homogeneous but not exceeding the lowest decomposition temperature of the reactants. Preferred temperatures are 250-400 DEG  F.  The rosin amine complex may be introduced as such into the reaction mixture or may be formed as a first step in the presence of the soap and then reacted with the said soap in the same reaction mix.  The rosin amine complex is defined as: (a) a phenoxide of a rosin amine or rosin ammonium phenoxide; (b) a metal rosin ammonium phenoxide complex; or (c) a complex metal ammine salt of a rosin amine.  The invention also comprises the complex double salts formed by reacting rosin amine complexes of types (b) or (c) above with the said soap in the presence of a quinoline such as quinoline, quinaldine, iso-quinoline, 4-chloroquinoline, 6- or 7-nitroquinoline, 6- or 8-methoxyquinoline, 2- or 4-methyl-2- or -4-hydroxyquinoline and 2- or 4- or 5- or 6- or 7- or 8-hydroxyquinoline.  The quinoline takes part in the reaction and forms part of the reaction product. The rosin ammonium phenoxides are prepared by reacting a rosin amine and a phenol as described in Specification 660,171.  The metal rosin ammonium phenoxide complexes are prepared by reacting a rosin ammonium phenoxide with a water-soluble salt of a metal e.g. nickel, cobalt, iron, chromium, aluminium, zinc, copper, mercury or silver) capable of forming complexes with ammonia.  The complex metal ammine salts of rosin amines are prepared by reacting a rosin amine with a water-soluble metal salt, such as those specified above, by the method described in Specification 640,402.  Specified rosin amines which may be used to form complex metal ammine salts are rosin amines made from wood or gum rosin, such as dehydrogenated, hydrogenated or polymerized rosin; amines derived from pure rosin acids such as abietyl amine, dehydroabietyl amine and tetrahydroabietyl amine; and secondary or tertiary rosin amines such as methyl or ethyl or dimethyl or diethyl or isopropyl or butyl or hydroxymethyl or hydroxyethyl or di-(hydroxyethyl) dehydroabietyl amine and the corresponding amines derived from abietic, dihydro- or tetra-hydroabietic or polymerized abietic acids.  The water-insoluble metal soaps used are soaps obtained from a metal or mixture of metals and a soap-forming acid or mixture of acids.  Specified metal components of the soaps are calcium, barium, magnesium, mercury, lead, cadmium, silver, thallium, manganese, cobalt, nickel, iron, copper, tin and aluminium. Specified soapforming acids are caproic, caprylic, capric, lauric, myristic, palmitic, stearic, oleic, linoleic, linolenic, palmitoleic, hydroxystearic, ricinoleic, naphthenic and abietic acids; and the mixed fatty acids derived from fish oils, lard, coconut oil, sesame oil, soybean oil, tung oil, corn oil, tall oil, carnauba, beeswax, spermaceti, candelilla wax and petroleum or other hydrocarbons. The metal soaps may be prepared from the acid and a metal salt in a preliminary stage of the reaction.  The complex double salts or compositions thereof may be used as fungicides (see Group VI) on plants, textiles, leather, paper and wood (see Group VIII) and when incorporated in varnishes, sealers, lacquers, paints, rosins and waxes (see Group III), and greases render them fungus-resistant.  In examples: (1) preparation of complex double salts of rosin ammonium phenoxides:-magnesium acetate and 2-ethylhexoic acid were heated together to give the metal soap, to the hot mixture were added equal parts of nonyl phenol and dehydroabietyl amine, the mixture reacted further until a clear solution was obtained and the whole diluted with xylol; in the reaction zinc oleate, copper oleate or nickel 2-ethylhexoate may replace magnesium 2-ethylhexoate, phenol or b -naphthol may replace nonyl phenol and dihydroabietyl amine or wood rosin amine may replace dehydroabietyl amine: (2) preparation of the complex double salts of metal rosin ammonium phenoxide complexes:-as in (1) but copper acetate or zinc acetate or mercury carbonate or nickel chloracetate or silver acetate added following the phenol and rosin amine: (3) preparation of complex double salts of metal ammine salts of rosin amine:-magnesium acetate and 2-ethylhexoic acid were heated together to give the metal soap, to the hot mixture was added dehydroabietyl amine followed by copper acetate, the mixture heated until a clear solution was obtained and the whole diluted with xylol; in the reaction zinc oleate or nickel 2-ethylhexoate may replace magnesium 2-ethylhexoate, dihydroabietyl amine or wood rosin amine may replace dehydroabietyl amine, and zinc acetate or mercuric acetate or silver nitrate may replace copper acetate: (4) the preparation of complex double salts of metal rosin ammonium phenoxide complexes in the presence of a quinoline:-magnesium acetate and 2-ethylhexoic acid were heated together to give the metal soap, to the hot mixture was added 8-hydroxyquinoline, nonyl phenol, dehydroabietyl amine and copper acetate, the resultant mixture reacted until a clear solution was obtained and the whole diluted with xylol; in the reaction nickel 2-ethylhexoate may replace magnesium 2-ethylhexoate, isoquinoline or 8-methoxy- or 4-chloro-quinoline may replace 8-hydroxyquinoline, phenol may replace nonylphenol,dihydroabietyl amine may replace dehydroabietyl amine and zinc acetate or mercury carbonate or nickel chloracetate or silver acetate may replace copper acetate: (5) preparation of complex double salts of complex metal ammine salts of rosin amines in the presence of a quinoline:-2-ethylhexoic acid and dehydroabietyl amine were heated together, 8-hydroxyquinoline and copper acetate were added, the mixture reacted until a clear solution was obtained, magnesium 2-ethylhexoate added, heating continued until a clear solution was obtained and the whole diluted with xylol; the product of the reaction is described as cupri-magnesium dehydroabietyl ammine 8-hydroxyquinolinium 2-ethylhexoate; in the reaction dihydroabietyl amine may replace dehydroabietyl amine, quinoline or isoquinoline or 8-methoxy- or 4-chloro-quinoline may replace 8-hydroxyquinoline, nickel 2-ethylhexoate may replace magnesium 2-ethylhexoate and zinc acetate or silver acetate or mercury carbonate or nickel chloracetate or chromic chloride may replace copper acetate.ALSO:The invention comprises complex double salts of rosin amine complexes, as hereinafter defined, and water-insoluble metal soaps.  They are prepared by reacting a rosin amine complex and a water-insoluble metal soap, in the presence or absence of a solvent, at an elevated temperature at least sufficient to render the mixture homogeneous but not exceeding the lowest decomposition temperature of the reactants. Reaction temperatures of 250-400 DEG  F. are preferred.  The rosin amine complex may be introduced as such into the reaction with the water-insoluble metal soap, or it may be formed as a first step in the presence of the water-insoluble metal soap and then reacted with the said soap in the same reaction mix.  The rosin amine complex is defined as: (a) a phenoxide of a rosin amine or rosin ammonium phenoxide; (b) a metal rosin ammonium phenoxide complex; or (c) a complex metal amine salt of a rosin amine.  The invention also comprises the complex double salts formed by reacting rosin amine complexes of types (b) or (c) above with the said soap in the presence of a quinoline such as quinoline, quinaldine, iso - quinoline, 4-chloroquinoline, 6 - or 7 - nitroquinoline, 6-or 8 - methoxyquinoline, 2 - or 4 - methyl - 2-or 4 - hydroxy - quinoline and 2 - or 4 - or 5-or 6 - or 7 - or 8 - hydroxyquinoline.  The quinoline takes part in the reaction and forms part of the reaction product.  The rosin ammonium phenoxides are prepared by reacting a rosin amine and a phenol as described in Specification 660,171.  The metal rosin ammonium phenoxide complexes are prepared by reacting a rosin ammonium phenoxide with a water-soluble salt of a metal (e.g. nickel, cobalt, iron, chromium, aluminium, zinc, copper, mercury or silver) capable of forming complexes with ammonia.  The complex metal ammine salts of rosin amines are prepared by reacting a rosin amine with a water-soluble metal salt, such as those specified above, by the method described in Specification 640,402, [Group IV (a)]. Specified rosin amines which may be used to form complex metal ammine salts are rosin amines made from wood or gum rosin, such as dehydrogenated, hydrogenated or polymerized rosin; amines derived from pure rosin acids such as abietyl amine, dehydroabietyl amine and tetrahydroabietyl amine; and secondary or tertiary rosin amines such as methyl or ethyl or dimethyl or diethyl or isopropyl or butyl or hydroxymethyl or hydroxyethyl or di(hydroxyethyl)dehydroabietyl amine and the corresponding amines derived from abietic, dihydro- or tetra-hydroabietic or polymerized abietic acids.  The water-insoluble metal soaps used are soaps obtained from a metal or mixture of metals and a soap-forming acid or mixture of acids.  Specified metal components of the soaps are calcium, barium, magnesium, mercury, lead, cadmium, silver, thallium, manganese, cobalt, nickel, iron, copper, tin and aluminium.  Specified soap-forming acids are caproic, caprylic, capric, lauric, myristic, palmitic, stearic, oleic, linoleic, linolenic, palmitoleic, hydroxystearic, ricinoleic, naphthenic and abietic acids; and the mixed fatty acids derived from fish oils, lard, coconut oil, sesame oil, soybean oil, tung oil, corn oil, tall oil, carnauba, beeswax, spermaceti, candelilla wax and petroleum or other hydrocarbons. The metal soaps may be prepared from the acid and a metal salt in a preliminary